Process for imparting stain resistance to fibers and to anti-staining agents for use in the process

Abstract

This invention relates to novel compositions for imparting stain resistance to fibers, which composition comprises a phenolic or naphtholic resin.

What is claimed is: 
     
       1. A process for imparting stain resisting properties to fibers formed from thermoplastic polymers, said process comprising: (a) treating said fibers with a composition comprising an effective carrier and a stain resisting effective amount of one or more condensation products of the Formula I:   P--Z--X--Z--X--Z--P;                                       Formula I        and   (b) annealing said treated fiber; wherein: Z is a divalent moiety of the formulas: ##STR4##  wherein: P is a hydrogen, --OH or a moiety of the formula --X-- OH;   m and o are the same or different and are positive whole numbers from 0 to 3 with the proviso that the sum of o and m at each occurrence is equal to 3;   u and v are the same or different at each occurrence and are positive whole numbers from 0 to 5 with the proviso that the sum of u and v at each occurrence is 5;   --X-- is a divalent organic radical;   R is the same or different at each occurrence and is selected from the group consisting of alkyl, aryloxy, alkoxy, aryl, hydroxy, and methylol; and   n is a positive whole number.     
     
     
       2. A process according to claim 1 wherein said composition comprises a phenol condensation product of Formula I. 
     
     
       3. A process according to claim 2 wherein X is substituted or unsubstituted methylene or 1,4-phenyldimethylene, wherein permissible substituents are alkyl having from 1 to about 10 carbon atoms, halogen, and furyl. 
     
     
       4. A process according to claim 3 wherein X is a moiety of the formula: ##STR5## where R 1  is hydrogen or alkyl. 
     
     
       5. A process according to claim 2 wherein n is from 1 to about 10. 
     
     
       6. A process according to claim 5 wherein n is from 1 to about 4. 
     
     
       7. A process according to claim 2 wherein: m is 0 or 1; and   o is 2 to 3.   
     
     
       8. A process according to claim 7 wherein: m is 0; and   o is 3.   
     
     
       9. A process according to claim 2 wherein R is alkyl. 
     
     
       10. A process according to claim 9 wherein R is methyl or ethyl. 
     
     
       11. A process according to claim 2 which further comprises treating said fiber with one or more other fiber-treating agents. 
     
     
       12. A process according to claim 11 wherein said other fiber-treating agent is an anti-soiling agent. 
     
     
       13. A process according to claim 12 wherein said anti-soiling agent is selected from the group consisting of compounds having the formula: ##STR6## wherein the attachment of the fluorinated radicals and the radicals CO 2  B to the nucleus is in asymmetrical positions with respect to rotation about the axis through the center of the nucleus; wherein "X" is fluorine, or perfluoroalkoxy of 1 to 6 carbon atoms, and m has arithmetic mean between 2 and 20; n is zero or unity; "W" and "Y" are alkylene, cycloalkylene or alkyleneoxy radicals of combined chain length from 2 to 20 atoms: (CF 2 ) m  and "Y" have each at least 2 carbon atoms in the main chain; "Z" is oxygen and p is 1, or "Z" is nitrogen and p is 2; q is an integer of at least 2 but not greater than 5; "B" is CH 2  RCHOH or is CH 2  RCHOCH 2  RCHOH where "R" is hydrogen or methyl, or "B" is CH 2  CH(OH)CH 2  Q where Q is halogen, hydroxy, or nitrile; or " B" is CH 2  CH(OH)CH 2  OCH 2  CH(OH)CH 2  Q; and r is an integer of at least 1 but not greater than q; and X(CF 2 ) m , W and Y are straight chains, branched chains or cyclic; and wherein the substituent chains of the active general formulas are the same or different; said compound being capable, upon contact thereof-as a solution or dispersion-with fibers of polyethylene terephthalate or of nylon and heating, of imparting water and oil repellency to such fibers. 
     
     
       14. A process of claim 13 being a trimellitate, a pyromellitate, of a bis(N-N-disubstituted amide)/ester of trimellitic acid or of pyromellitic acid, wherein each fluorinated radical, of formula X(CF 2 ) m  W(CONH) m  Y, has a main chain contacting at least six carbon atoms and contains at least four perfluorinated carbon atoms in the radical. 
     
     
       15. A process according to claim 14 wherein the fluorinated moiety in said fluorinated radicals has formula CF 3  (CF 2 ) m  or (CF 3 ) 2  CFO(CF 2 ) m  ; m having independently at each occurrence any value from 5 to 9 and m having independently at each occurrence any value from 5 to 9 and m having independently at each occurrence any value from 2 to 16, (CF 2 ) m  and (CF 2 ) m  being straight chains; and wherein said B radicals are CH 2  CH 2  OH, CH 2  CH(OH)CH 2  Cl, CH 2  CH(OH)CH 2  OH or CH 2  CH(OH)CH 2  Br. 
     
     
       16. A process according to claim 14 being a mixture of para and meta substituted pyromellitic acid position isomers wherein overall the two fluorinated raidcals have the same formula and the two radicals B have the same formula. 
     
     
       17. A process according to claim 13 wherein said compound is a pyromellitate; wherein said fluorinated radicals have formula CF 3  (CF 2 ) m  CH 2  CH 2  -- with m being independently at each occurrence an integer from 2 to 16; wherein --(CF 2 ) m  -- and --(CF 2 ) m  -- are straight chains; and wherein said B radicals have formula CH 2  CH 2  OH, CH 2  CH(OH)CH 2  Cl, CH 2  CH(OH)CH 2  OH or CH 2  CH(OH)CH 2  Br. 
     
     
       18. A process according to claim 17 wherein said pyromellitate is the metal isomer and m is 5 to 9 or m is 2 or 4. 
     
     
       19. A process according to claim 12 wherein said other fiber-treating agent is selected from the group consisting of oligomer containing mixtures produced by a process which comprises: (a) reacting pyromellitic dianhydride with fluorinated alcohol at a mole ratio of fluorinated alcohol to pyromellitic dianhydride between about 1:0,55 and about 1:1.0 to form a partially esterfied product having fluorinated ester groups, free acid groups and anhydride groups; and   (b) reacting the partially esterfied product with an oxirane compound selected from the group consisting of epichlorohydrin, epibromohydrin and propylene oxide in an amount sufficient to cause essentially all of the free acid groups and anhydride groups to be esterfied.   
     
     
       20. A process according to claim 19 wherein said fluorinated alcohol is of the formula: CF 3  (CF 2 ) p  R'OH wherein R' is alkylene of 2-6 carbons and p is an integer of 3-15. 
     
     
       21. A process according to claim 20 wherein said fluorinated alcohol is a mixture of compounds of the formula CF 3  CF 2  (CF 2  CF 2 ) n  CH 2  CH 2  OH with n being from 1 to 6. 
     
     
       22. A process according to claim 21 wherein n is from 2 to 5. 
     
     
       23. A process according to claim 19 wherein said mole ratio is between about 1:0.6 and about 1:0.85. 
     
     
       24. A process according to claim 19 wherein said mole ratio is between about 1:0.65 and about 1:0.75. 
     
     
       25. A process according to claim 21 wherein said other fiber-treating agent is selected from the group consisting of oligomeric compounds produced by a process comprising: (a) reacting pyromellitic dianhydride with fluorinated alcohol at a mole ratio of about two moles of fluorinated alcohol per mole of pyromellitic dianhydride to produce a pyromellitate having two fluorinated ester moieties and two carboxylic acid moieties;   (b) reacting said pyromellitate of step (a) with an excess of an oxirane compound selected from the group consisting of epichlorohydrin, epibromohydrin, and propylene oxide in the presence of additional pyromellitic dianhydride to produce said organic mixture comprising oligomeric compounds; wherein said oxirane compounds react with said carboxylic acid moieties to produce an ester having a primary or secondary alcohol, and wherein said alcohol reacts with said additional pyromellitic dianhydride to produce ester-linking moieties and carboxylic acid moieties capable of reacting with said oxirane compound to produce additional esters having primary or secondary alcohols.   
     
     
       26. A process according to claim 25 wherein said excess pyromellitic dianhydride is added to a reaction medium in said step (b) when about 50% to about 100% of the carboxylic acid moieties have been esterified. 
     
     
       27. A process according to claim 26 wherein said excess pyromellitic dianhydride is added to a reaction medium in said step (b) when about 85% to about 95% of the carboxylic acid moieties have been esterfied. 
     
     
       28. A process according to claim 25 wherein said additional pyromellitic dianhydride is added to a reaction medium in said step (b) simultaneously with the oxirance compound. 
     
     
       29. The process of claim 25 wherein said fluorinated alcohols is of the formula: CF 3  (CF 2 ) p  R'OH wherein R' is alkylene of 2-6 carbons and p is an integer of 3-15. 
     
     
       30. A process according to claim 1 which further comprises annealing said treated fiber by heating at a temperature above the glass transition temperature of the thermoplastic polymer forming said fiber and below the degradation temperature of the thermoplastic polymer forming said fiber and the condensation products. 
     
     
       31. A process according to claim 30 wherein said treated fiber is heated at a temperature of from about 100° C. to about 220° C. 
     
     
       32. A process according to claim 11 wherein said treating steps are carried out sequentially. 
     
     
       33. A process according to claim 32 wherein said treating steps are carried out simultaneously. 
     
     
       34. A process according to claim 1 wherein said fibers are formed from a polyester or a polyamide. 
     
     
       35. A process according to claim 34 wherein said fiber is formed from a polyamide. 
     
     
       36. A process according to claim 35 wherein said polyamide is selected from the group consisting of nylon 6 and nylon 66. 
     
     
       37. A process according to claim 35 wherein said polyamide is nylon 6.